CN102079505B - Ordered structure array of two-dimensional hollow balls and preparing method thereof - Google Patents
Ordered structure array of two-dimensional hollow balls and preparing method thereof Download PDFInfo
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Abstract
The present invention discloses an ordered structure array of two-dimensional hollow balls and a preparing method thereof. The array is a single-layer hollow ball array which is provided with an ordered hexagonal arrangement on a substrate. The outer diameter of each hollow ball in the single-layer hollow ball array is 220nm-10.8mu m. An outer surface of each ball is a rough surface. Each hollow ball is composed of a gold metal inner surface and metal gold or polypyrrole or zinc oxide which is coated on the gold metal inner surface. The rough surface is composed of particle-shaped objects or vertical rod-shaped objects. The method comprises the following steps: performing ion sputtering on a conductive substrate which is provided with a single-layer colloid crystal template for depositinga gold film and obtaining a gold film wall array; then placing the conductive substrate which is adhered with the gold film array into electrolyte; performing electrodeposition for 10s-3h with a deposition current density of -1.0-1.0Ma/cm2 for obtaining a complex array; then placing the complex array into a dichloromethane solvent for removing polystyrene colloid balls and preparing the ordered structure array of the two-dimensional hollow balls. The ordered structure array of the two-dimensional hollow balls can be widely used for the following fields: medicament engineering, cosmetic, biotechnology, photocatalysis, photonic device, etc.
Description
Technical field
The present invention relates to a kind of hollow ball ordered structure array and preparation method, especially a kind of two-dimentional hollow ball ordered structure array and preparation method thereof.
Background technology
Hollow ball structure, as carrier and inner pressurd vessel, little reaction chamber etc., because its special structure and surface nature have caused that people note widely, it has important use in many-sides such as medicine engineering, cosmetics, biotechnology, photocatalysis and photonic devices and is worth.The application of hollow ball is relevant with its material category and physical dimension, also with the fine structure close association of spherical shell layer.The hollow ball of hierarchy, its spherical shell are made of as nano particle, nanometer rods and nanometer sheet the junior unit of nanoscale, and this will construct the device of nano material and play an important role.In the recent period, one of synthetic focus that becomes the nano materials research field of hierarchy system.As a kind of " two dimension, three-dimensional order nano structure metal materials and the preparation method that are constituted by hollow metal sphere " who discloses among the disclosed Chinese invention patent ublic specification of application CN1487108A on April 7th, 2004.Two and three dimensions ordered nano-structure metal material and preparation method that it is intended to provide a kind of medium ball by the metal parcel or hollow metal spherical shell to form; Wherein, the sequential 2 D nano structure metal materials is to be arranged by six sides at substrate by hollow metal sphere to form two-dimensional array, and Metal Ball wherein can be gold or silver etc., and the preparation method is template with the colloidal crystal, adopt first wicking sensitization, again the technology of chemical plating metal.But, no matter be the sequential 2 D nano structure metal materials, or its preparation method, all exist weak point, at first, the hollow metal sphere that constitutes the sequential 2 D nano structure metal materials only be single-wall structure, rather than inside and outside wall has heteroid hollow ball, can obtainable superior function and the purposes of uniqueness thereby limited it; Secondly, the preparation method can't obtain inside and outside wall and have heteroid hollow ball.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of inside and outside wall to have heteroid two-dimentional hollow ball ordered structure array for overcoming weak point of the prior art.
Another technical problem that the present invention will solve is for providing a kind of preparation method with two-dimentional hollow ball ordered structure array of universality.
For solving technical problem of the present invention, the technical scheme that adopts is: two-dimentional hollow ball ordered structure array comprises the individual layer hollow ball array of the orderly six sides arrangement that is equipped with on the substrate, particularly,
Described substrate is conductive substrates, and the ball overall diameter of the hollow ball on the described conductive substrates in the hollow ball array is 220nm～10.8 μ m, and the outer surface of ball is matsurface;
Described hollow ball is made of the metallic gold that is covered with on metallic gold inwall and its or polypyrrole or cadmium sulfide or zinc oxide, wherein, the thickness of metallic gold inwall is 5～15nm, and the thickness of metallic gold or polypyrrole or cadmium sulfide is 5～50nm, and the thickness of zinc oxide is 200～800nm;
Described matsurface is made of the club of granular substance or setting, the grain diameter of described granular substance is 10～50nm, it is made of metallic gold or polypyrrole or cadmium sulfide, the rod axle of described club is perpendicular with the centre of sphere of described hollow ball, its rod length is that 200～800nm, excellent diameter are 80～160nm, and it is made of zinc oxide.
As the further improvement of two-dimentional hollow ball ordered structure array, described individual layer hollow ball array is loose arrangement.
For solving another technical problem of the present invention, another technical scheme that adopts is: the preparation method of two-dimentional hollow ball ordered structure array comprises that the colloid monolayer crystal template that the polystyrene colloid ball that will by bulb diameter be 200～10000nm constitutes places on the conductive substrates, and the preparation of electrolyte, particularly completing steps is as follows:
Step 1, it is ion sputtering deposition gold film under 5～10Pa that the conductive substrates that has colloid monolayer crystal template on it is placed pressure, obtains golden membranous wall array;
Step 2, earlier the conductive substrates of having golden membranous wall array it on being placed temperature is electrolyte under 10～80 ℃, as working electrode, is-1.0～1.0mA/cm in depositing current density with it
2Under adopt three-electrode method electro-deposition 10s～3h, obtain the complex array, again the complex array is placed dichloromethane solvent to remove the polystyrene colloid ball, make two-dimentional hollow ball ordered structure array.
Further improvement as the preparation method of two-dimentional hollow ball ordered structure array, it is described before the conductive substrates that it is had colloid monolayer crystal template is carried out ion sputtering deposition gold film, be placed on earlier in the argon gas atmosphere, use plasma to its etching 10～45min; When described electrolyte was metallic gold electrolyte, it was that the gold chloride of 12g/L, the ethylenediamine tetra-acetic acid of 5g/L, the sodium sulfite of 160g/L and dipotassium hydrogen phosphate and the water of 30g/L mix by concentration, and the current density during the electrodeposit metals gold is-0.4mA/cm
2, temperature is 25 ℃; When described electrolyte was polypyrrole electrolyte, it was that pyrroles's aqueous phase solution of 0.1M and the neopelex aqueous phase solution of 0.1M mix by concentration, and the current density during the electro-deposition polypyrrole is 0.5mA/cm
2, temperature is 25 ℃; When described electrolyte was cadmium sulfide electrolyte, it was that the caddy aqueous phase solution of 0.05M and the thioacetamide aqueous phase solution of 0.1M mix by concentration, and the current density during the electro-deposition cadmium sulfide is-0.025mA/cm
2, temperature is 70 ℃; When described electrolyte was zinc oxide electrolyte, it was that zinc nitrate/ammoniacal liquor aqueous phase solution of 0.05M constitutes by concentration, and the current density during electro deposition oxidation zinc is-1.0mA/cm
2, temperature is 70 ℃; During described three-electrode method electro-deposition is graphite electrode to electrode, and reference electrode is saturated calomel electrode; Described conductive substrates is electro-conductive glass or conductive rubber or monocrystalline silicon or metal.
Beneficial effect with respect to prior art is, one, use field emission scanning electron microscope and x-ray diffractometer to characterize respectively to the different products that make, by its result as can be known, product is the individual layer hollow ball array that places orderly six sides on the conductive substrates to arrange, being two-dimentional hollow ball ordered structure array, is closely to arrange or loose arrangement between the hollow ball in the array, and the ball overall diameter of hollow ball is 220nm～10.8 μ m.Hollow ball is made of the metallic gold that is covered with on metallic gold inwall and its or polypyrrole or cadmium sulfide or zinc oxide, wherein, the thickness of metallic gold inwall is 5～15nm, and the thickness of metallic gold or polypyrrole or cadmium sulfide is 5～50nm, and the thickness of zinc oxide is 200～800nm.The outer surface of hollow ball is matsurface, its club by granular substance or setting constitutes, the grain diameter of granular substance wherein is 10～50nm, it is made of metallic gold or polypyrrole or cadmium sulfide, the rod axle of club is perpendicular with the centre of sphere of hollow ball, its rod length is that 200～800nm, excellent diameter are 80～160nm, and it is made of zinc oxide.Conductive substrates is electro-conductive glass or conductive rubber or monocrystalline silicon or metal; They are two years old, this two-dimentional hollow ball ordered structure array that is comprising three kinds of different structure sizes with macro-scale architectural feature, both had the intrinsic character of array component units nano material itself, not isostructure because of the unit inside and outside wall changes to some extent to its original character again, be expected to realize some specific functions, also can produce the new performance that some isolated units do not have because of the coupling effect between the unit, will have a wide range of applications in the field of many unknowns, as the SERS that can obtain excellent properties and as super-hydrophobic backing material; Its three, the preparation method is science, effectively not only, also has universality.Method adopts the polystyrene colloid ball of different-diameter to constitute colloid monolayer crystal template, the effective regulation and control to two-dimentional hollow ball ordered structure array hollow core bulb diameter have been realized, method is carried out organic combination with ion sputtering method and electrodeposition process, obtained to have the hollow ball of different inside and outside wall structures in the conductive substrates that has the crystal template, method optionally prepares needed material, as uses other metal, semiconductor, conductive organic matter to wait to constitute two-dimentional hollow ball ordered structure array; Its four, pollution-free in the preparation process, belong to green synthesis techniques, and materials are few, the production efficiency height is suitable for large-scale industrial production.
Further embodiment as beneficial effect, the one, before the conductive substrates that it is had colloid monolayer crystal template is carried out ion sputtering deposition gold film, preferably be placed in the argon gas atmosphere earlier, use plasma to its etching 10～45min, obtained to be the product of loose arrangement between the hollow ball on it, be beneficial to application scenario or the field of expanding product; The 2nd, when electrolyte is preferably metallic gold electrolyte, it is that the gold chloride of 12g/L, the ethylenediamine tetra-acetic acid of 5g/L, the sodium sulfite of 160g/L and dipotassium hydrogen phosphate and the water of 30g/L mix by concentration, and the current density during the electrodeposit metals gold is preferably-0.4mA/cm
2, temperature is preferably 25 ℃, and when electrolyte was preferably polypyrrole electrolyte, it was that pyrroles's aqueous phase solution of 0.1M and the neopelex aqueous phase solution of 0.1M mix by concentration, and the current density during the electro-deposition polypyrrole is preferably 0.5mA/cm
2, temperature is preferably 25 ℃, and when electrolyte was preferably cadmium sulfide electrolyte, it was that the caddy aqueous phase solution of 0.05M and the thioacetamide aqueous phase solution of 0.1M mix by concentration, and the current density during the electro-deposition cadmium sulfide is preferably-0.025mA/cm
2, temperature is preferably 70 ℃, and when electrolyte was preferably zinc oxide electrolyte, it was that zinc nitrate/ammoniacal liquor aqueous phase solution of 0.05M constitutes by concentration, and the current density during electro deposition oxidation zinc is preferably-1.0mA/cm
2, temperature is preferably 70 ℃, not only lays a good foundation for the two-dimentional hollow ball ordered structure array that makes metallic gold, polypyrrole, cadmium sulfide and zinc oxide formation, has guaranteed that also different materials all can be assembled into the outer surface of golden membranous wall array equably; The 3rd, during the three-electrode method electro-deposition electrode is preferably graphite electrode, reference electrode is preferably saturated calomel electrode, all is beneficial to the enforcement of electro-deposition; The 4th, conductive substrates is preferably electro-conductive glass or conductive rubber or monocrystalline silicon or metal, except conductive substrates is had the leeway of bigger selection, also makes the easier enforcement of preparation technology and flexible.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 is to be that the product of metallic gold uses one of result that field emission scanning electron microscope (SEM) characterizes to the hollow ball outer surface that makes.Wherein, the SEM photo of the product that Figure 1A makes for the colloid monolayer crystal template that constitutes based on the polystyrene colloid ball that by bulb diameter is 2000nm, by it as can be known, product is the individual layer hollow ball array that orderly six sides arrange; Figure 1B is the high-resolution SEM photo of product shown in Figure 1A, can be seen the matsurface of the outer surface of product for being made of granular substance by it; Fig. 1 C is the SEM photo of the oblique side-looking of product shown in Figure 1A, and it is the same with Figure 1A, and having confirmed product is the individual layer hollow ball array that orderly six sides arrange; Fig. 1 D is the high-resolution SEM photo after the ball breakage in the product shown in Figure 1A, can be seen that by it ball in product is hollow ball, the thickness of hollow ball shell is about 47 nanometers, granular substance not only has been covered with the outer surface of hollow ball, but also has been covered with the surface of conductive substrates.
Fig. 2 is to be that the product of polypyrrole uses one of result that field emission scanning electron microscope characterizes to the hollow ball outer surface that makes.Wherein, the high-resolution SEM photo of the product that Fig. 2 A makes for the colloid monolayer crystal template that constitutes based on the polystyrene colloid ball that by bulb diameter is 2000nm, Fig. 2 B is the SEM photo of product shown in Fig. 2 A, by Fig. 2 A and Fig. 2 B as can be known, product is the individual layer hollow ball array that orderly six sides arrange, the matsurface that the granular substance that the outer surface of hollow ball is served as reasons thinner constitutes.
Fig. 3 is to be that the product of cadmium sulfide uses one of result that field emission scanning electron microscope and X-ray diffraction (XRD) instrument characterize respectively to the hollow ball outer surface that makes.Wherein, the high-resolution SEM photo of the product that Fig. 3 A makes for the colloid monolayer crystal template that constitutes based on the polystyrene colloid ball that by bulb diameter is 2000nm, by it as can be known, product is the individual layer hollow ball array that orderly six sides arrange, the matsurface of the outer surface of hollow ball wherein for being made of granular substance; Fig. 3 B is the XRD spectra of product shown in Fig. 3 A, and by it as can be known, product is made of metallic gold and cadmium sulfide.
Fig. 4 is to be that the product of zinc oxide uses one of result that field emission scanning electron microscope characterizes to the hollow ball outer surface that makes.Wherein, the SEM photo of the product that Fig. 4 A makes for the colloid monolayer crystal template that constitutes based on the polystyrene colloid ball that by bulb diameter is 2000nm, Fig. 4 B is the high-resolution SEM photo of product shown in Fig. 4 A, by Fig. 4 A and Fig. 4 B as can be known, product is constituted by being erected in by club on the individual layer hollow ball array that orderly six sides arrange.
Fig. 5 is to be that the product of metallic gold uses one of result that field emission scanning electron microscope characterizes to the hollow ball outer surface that makes.Wherein, Fig. 5 A and Fig. 5 B are the colloid monolayer crystal template that constitutes based on the polystyrene colloid ball that by bulb diameter is 2000nm, and behind plasma etching and the SEM photo of the product that makes, by it as can be known, product is the individual layer hollow ball array that orderly six sides arrange, and is loose arrangement between hollow ball wherein; Fig. 5 C and Fig. 5 D are the high-resolution SEM photo of product shown in Fig. 5 A, can be seen by it, and the matsurface of the outer surface of product for being constituted by granular substance, granular substance not only has been covered with the outer surface of hollow ball, but also has been covered with the surface of conductive substrates.
The specific embodiment
At first make or buy from market the polystyrene colloid ball that bulb diameter is 200～10000nm with conventional method; Metallic gold electrolyte as electrolyte, polypyrrole electrolyte, cadmium sulfide electrolyte and zinc oxide electrolyte, wherein, metallic gold electrolyte is the gold chloride of 12g/L by concentration, the ethylenediamine tetra-acetic acid of 5g/L, the sodium sulfite of 160g/L and the dipotassium hydrogen phosphate of 30g/L and water mix, polypyrrole electrolyte is that pyrroles's aqueous phase solution of 0.1M and the neopelex aqueous phase solution of 0.1M mix by concentration, cadmium sulfide electrolyte is that the caddy aqueous phase solution of 0.05M and the thioacetamide aqueous phase solution of 0.1M mix by concentration, and zinc oxide electrolyte is that zinc nitrate/ammoniacal liquor aqueous phase solution of 0.05M constitutes by concentration; Electro-conductive glass, conductive rubber, monocrystalline silicon and metal as conductive substrates.Then,
Embodiment 1
The concrete steps of preparation are:
Step 1, with have on it by bulb diameter be the conductive substrates of the colloid monolayer crystal template that constitutes of the polystyrene colloid ball of 2000nm to place pressure be under the 5Pa, ion sputtering deposition thickness is one deck gold film of 5nm, obtains golden membranous wall array; Wherein, conductive substrates is electro-conductive glass.
Step 2, earlier the conductive substrates of having golden membranous wall array it on being placed temperature is electrolyte under 10 ℃, with it as working electrode, in depositing current density be-1.0mA/cm
2Under adopt three-electrode method electro-deposition 10s, obtain the complex array; Wherein, electrolyte is metallic gold electrolyte, and during the three-electrode method electro-deposition is graphite electrode to electrode, and reference electrode is saturated calomel electrode.The complex array is placed dichloromethane solvent to remove the polystyrene colloid ball, making and being similar to the ball inwall shown in Figure 1A, Figure 1B, Fig. 1 C and Fig. 1 D is that metallic gold, outer surface of ball are the two-dimentional hollow ball ordered structure array of granular metal gold again.
Perhaps, be before the conductive substrates of the colloid monolayer crystal template that constitutes of the polystyrene colloid ball of 2000nm is carried out ion sputtering deposition gold film it being had by bulb diameter, be placed in the argon gas atmosphere earlier, after using plasma to its etching 10min, carry out the technical process of above-mentioned steps 1 and step 2 again, then making and being similar to the ball inwall shown in Fig. 5 A, Fig. 5 B, Fig. 5 C and Fig. 5 D is that metallic gold, outer surface of ball are the two-dimentional hollow ball ordered structure array of granular metal gold.
Embodiment 2
The concrete steps of preparation are:
Step 1, with have on it by bulb diameter be the conductive substrates of the colloid monolayer crystal template that constitutes of the polystyrene colloid ball of 2000nm to place pressure be under the 6Pa, ion sputtering deposition thickness is one deck gold film of 8nm, obtains golden membranous wall array; Wherein, conductive substrates is electro-conductive glass.
Step 2, earlier the conductive substrates of having golden membranous wall array it on being placed temperature is electrolyte under 25 ℃, with it as working electrode, in depositing current density be-0.4mA/cm
2Under adopt three-electrode method electro-deposition 200s, obtain the complex array; Wherein, electrolyte is metallic gold electrolyte, and during the three-electrode method electro-deposition is graphite electrode to electrode, and reference electrode is saturated calomel electrode.The complex array is placed dichloromethane solvent to remove the polystyrene colloid ball, the ball inwall that makes shown in Figure 1A, Figure 1B, Fig. 1 C and Fig. 1 D is that metallic gold, outer surface of ball are the two-dimentional hollow ball ordered structure array of granular metal gold again.
Perhaps, be before the conductive substrates of the colloid monolayer crystal template that constitutes of the polystyrene colloid ball of 2000nm is carried out ion sputtering deposition gold film it being had by bulb diameter, be placed in the argon gas atmosphere earlier, after using plasma to its etching 17min, carry out the technical process of above-mentioned steps 1 and step 2 again, the ball inwall that then makes shown in Fig. 5 A, Fig. 5 B, Fig. 5 C and Fig. 5 D is that metallic gold, outer surface of ball are the two-dimentional hollow ball ordered structure array of granular metal gold.
Embodiment 3
The concrete steps of preparation are:
Step 1, with have on it by bulb diameter be the conductive substrates of the colloid monolayer crystal template that constitutes of the polystyrene colloid ball of 2000nm to place pressure be under the 8Pa, ion sputtering deposition thickness is one deck gold film of 10nm, obtains golden membranous wall array; Wherein, conductive substrates is electro-conductive glass.
Step 2, earlier the conductive substrates of having golden membranous wall array it on being placed temperature is electrolyte under 50 ℃, with it as working electrode, in depositing current density be-0.025mA/cm
2Under adopt three-electrode method electro-deposition 30min, obtain the complex array; Wherein, electrolyte is metallic gold electrolyte, and during the three-electrode method electro-deposition is graphite electrode to electrode, and reference electrode is saturated calomel electrode.The complex array is placed dichloromethane solvent to remove the polystyrene colloid ball, making and being similar to the ball inwall shown in Figure 1A, Figure 1B, Fig. 1 C and Fig. 1 D is that metallic gold, outer surface of ball are the two-dimentional hollow ball ordered structure array of granular metal gold again.
Perhaps, be before the conductive substrates of the colloid monolayer crystal template that constitutes of the polystyrene colloid ball of 2000nm is carried out ion sputtering deposition gold film it being had by bulb diameter, be placed in the argon gas atmosphere earlier, after using plasma to its etching 25min, carry out the technical process of above-mentioned steps 1 and step 2 again, then making and being similar to the ball inwall shown in Fig. 5 A, Fig. 5 B, Fig. 5 C and Fig. 5 D is that metallic gold, outer surface of ball are the two-dimentional hollow ball ordered structure array of granular metal gold.
Embodiment 4
The concrete steps of preparation are:
Step 1, with have on it by bulb diameter be the conductive substrates of the colloid monolayer crystal template that constitutes of the polystyrene colloid ball of 2000nm to place pressure be under the 9Pa, ion sputtering deposition thickness is one deck gold film of 13nm, obtains golden membranous wall array; Wherein, conductive substrates is electro-conductive glass.
Step 2, earlier the conductive substrates of having golden membranous wall array it on being placed temperature is electrolyte under 70 ℃, as working electrode, is 0.5mA/cm in depositing current density with it
2Under adopt three-electrode method electro-deposition 1h, obtain the complex array; Wherein, electrolyte is metallic gold electrolyte, and during the three-electrode method electro-deposition is graphite electrode to electrode, and reference electrode is saturated calomel electrode.The complex array is placed dichloromethane solvent to remove the polystyrene colloid ball, making and being similar to the ball inwall shown in Figure 1A, Figure 1B, Fig. 1 C and Fig. 1 D is that metallic gold, outer surface of ball are the two-dimentional hollow ball ordered structure array of granular metal gold again.
Perhaps, be before the conductive substrates of the colloid monolayer crystal template that constitutes of the polystyrene colloid ball of 2000nm is carried out ion sputtering deposition gold film it being had by bulb diameter, be placed in the argon gas atmosphere earlier, after using plasma to its etching 33min, carry out the technical process of above-mentioned steps 1 and step 2 again, then making and being similar to the ball inwall shown in Fig. 5 A, Fig. 5 B, Fig. 5 C and Fig. 5 D is that metallic gold, outer surface of ball are the two-dimentional hollow ball ordered structure array of granular metal gold.
Embodiment 5
The concrete steps of preparation are:
Step 1, with have on it by bulb diameter be the conductive substrates of the colloid monolayer crystal template that constitutes of the polystyrene colloid ball of 2000nm to place pressure be under the 10Pa, ion sputtering deposition thickness is one deck gold film of 15nm, obtains golden membranous wall array; Wherein, conductive substrates is electro-conductive glass.
Step 2, earlier the conductive substrates of having golden membranous wall array it on being placed temperature is electrolyte under 80 ℃, as working electrode, is 1.0mA/cm in depositing current density with it
2Under adopt three-electrode method electro-deposition 3h, obtain the complex array; Wherein, electrolyte is metallic gold electrolyte, and during the three-electrode method electro-deposition is graphite electrode to electrode, and reference electrode is saturated calomel electrode.The complex array is placed dichloromethane solvent to remove the polystyrene colloid ball, making and being similar to the ball inwall shown in Figure 1A, Figure 1B, Fig. 1 C and Fig. 1 D is that metallic gold, outer surface of ball are the two-dimentional hollow ball ordered structure array of granular metal gold again.
Perhaps, be before the conductive substrates of the colloid monolayer crystal template that constitutes of the polystyrene colloid ball of 2000nm is carried out ion sputtering deposition gold film it being had by bulb diameter, be placed in the argon gas atmosphere earlier, after using plasma to its etching 45min, carry out the technical process of above-mentioned steps 1 and step 2 again, then making and being similar to the ball inwall shown in Fig. 5 A, Fig. 5 B, Fig. 5 C and Fig. 5 D is that metallic gold, outer surface of ball are the two-dimentional hollow ball ordered structure array of granular metal gold.
Selecting bulb diameter more respectively for use is that the polystyrene colloid ball of the arbitrary bulb diameter among 200～10000nm is made colloid monolayer crystal template, select metallic gold electrolyte or polypyrrole electrolyte or cadmium sulfide electrolyte or zinc oxide electrolyte as electrolyte for use, and select electro-conductive glass or conductive rubber or monocrystalline silicon or metal as conductive substrates for use, repeat above-described embodiment 1～5, same:
Making as or be similar to the ball inwall shown in Figure 1A～Fig. 1 D is that metallic gold, outer surface of ball are the two-dimentional hollow ball ordered structure array of granular metal gold.Perhaps, earlier the colloid monolayer crystal template on the conductive substrates being used plasma etching, is that metallic gold, outer surface of ball are the two-dimentional hollow ball ordered structure array of granular metal gold and make as or be similar to the ball inwall shown in Fig. 5 A～Fig. 5 B.
Or to make as or be similar to the ball inwall shown in Fig. 2 A～Fig. 2 B be that metallic gold, outer surface of ball are the two-dimentional hollow ball ordered structure array of graininess polypyrrole.Perhaps, earlier the colloid monolayer crystal template on the conductive substrates being used plasma etching, is that metallic gold, outer surface of ball are the two-dimentional hollow ball ordered structure array of graininess polypyrrole and make as or be similar to the ball inwall shown in Fig. 5 A～Fig. 5 B.
Or make as or be similar to Fig. 3 A and as or to be similar to the ball inwall shown in the curve among Fig. 3 B be that metallic gold, outer surface of ball are the two-dimentional hollow ball ordered structure array of graininess cadmium sulfide.Perhaps, earlier the colloid monolayer crystal template on the conductive substrates being used plasma etching, is that metallic gold, outer surface of ball are the two-dimentional hollow ball ordered structure array of graininess cadmium sulfide and make as or be similar to the ball inwall shown in Fig. 5 A～Fig. 5 B.
Or to make as or be similar to the ball inwall shown in Fig. 4 A～Fig. 4 B be that metallic gold, outer surface of ball are the two-dimentional hollow ball ordered structure array of bar-shaped zinc oxide.Perhaps, earlier the colloid monolayer crystal template on the conductive substrates is used plasma etching, to be similar to the ball inwall shown in Fig. 5 A～Fig. 5 B be that metallic gold, outer surface of ball are the two-dimentional hollow ball ordered structure array of bar-shaped zinc oxide and make.
Obviously, those skilled in the art can carry out various changes and modification to two-dimentional hollow ball ordered structure array of the present invention and preparation method thereof and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (9)
1. two-dimentional hollow ball ordered structure array comprises the individual layer hollow ball array that orderly six sides that are equipped with on the substrate arrange, and it is characterized in that:
Described substrate is conductive substrates, and the ball overall diameter of the hollow ball on the described conductive substrates in the hollow ball array is 220nm～10.8 μ m, and the outer surface of ball is matsurface;
Described hollow ball is made of the polypyrrole that is covered with on metallic gold inwall and its or cadmium sulfide or zinc oxide, and wherein, the thickness of metallic gold inwall is 5～15nm, and the thickness of polypyrrole or cadmium sulfide is 5～50nm, and the thickness of zinc oxide is 200～800nm;
Described matsurface is made of the club of granular substance or setting, the grain diameter of described granular substance is 10～50nm, it is made of polypyrrole or cadmium sulfide, described club is erected on the individual layer hollow ball array of orderly six sides arrangement, its rod length is that 200～800nm, excellent diameter are 80～160nm, and it is made of zinc oxide.
2. two-dimentional hollow ball ordered structure array according to claim 1 is characterized in that individual layer hollow ball array is loose arrangement.
3. the preparation method of the described two-dimentional hollow ball ordered structure array of claim 1, comprise to be that the colloid monolayer crystal template that the polystyrene colloid ball of 200～10000nm constitutes places on the conductive substrates by bulb diameter, and the preparation of electrolyte, it is characterized in that completing steps is as follows:
Step 1, it is ion sputtering deposition gold film under 5～10Pa that the conductive substrates that has colloid monolayer crystal template on it is placed pressure, obtains golden membranous wall array;
Step 2, earlier the conductive substrates of having golden membranous wall array it on being placed temperature is electrolyte under 10～80 ℃, as working electrode, is-1.0～1.0mA/cm in depositing current density with it
2Under adopt three-electrode method electro-deposition 10s～3h, obtain the complex array, again the complex array is placed dichloromethane solvent to remove the polystyrene colloid ball, make two-dimentional hollow ball ordered structure array.
4. the preparation method of two-dimentional hollow ball ordered structure array according to claim 3, it is characterized in that before the conductive substrates that it is had colloid monolayer crystal template is carried out ion sputtering deposition gold film, be placed on earlier in the argon gas atmosphere, use plasma to its etching 10～45min.
5. according to the preparation method of claim 3 or 4 described two-dimentional hollow ball ordered structure arrays, when it is characterized in that electrolyte is polypyrrole electrolyte, it is that pyrroles's aqueous phase solution of 0.1M and the neopelex aqueous phase solution of 0.1M mix by concentration; Current density during the electro-deposition polypyrrole is 0.5mA/cm
2, temperature is 25 ℃.
6. according to the preparation method of claim 3 or 4 described two-dimentional hollow ball ordered structure arrays, when it is characterized in that electrolyte is cadmium sulfide electrolyte, it is that the caddy aqueous phase solution of 0.05M and the thioacetamide aqueous phase solution of 0.1M mix by concentration; Current density during the electro-deposition cadmium sulfide is-0.025mA/cm
2, temperature is 70 ℃.
7. according to the preparation method of claim 3 or 4 described two-dimentional hollow ball ordered structure arrays, when it is characterized in that electrolyte is zinc oxide electrolyte, it is that zinc nitrate/ammoniacal liquor aqueous phase solution of 0.05M constitutes by concentration; Current density during electro deposition oxidation zinc is-1.0mA/cm
2, temperature is 70 ℃.
8. according to the preparation method of claim 3 or 4 described two-dimentional hollow ball ordered structure arrays, when it is characterized in that the three-electrode method electro-deposition is graphite electrode to electrode, and reference electrode is saturated calomel electrode.
9. according to the preparation method of claim 3 or 4 described two-dimentional hollow ball ordered structure arrays, it is characterized in that conductive substrates is electro-conductive glass, or conductive rubber, or monocrystalline silicon, or metal.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910185811 CN102079505B (en) | 2009-12-01 | 2009-12-01 | Ordered structure array of two-dimensional hollow balls and preparing method thereof |
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| CN102874742A (en) * | 2011-07-15 | 2013-01-16 | 中国科学院合肥物质科学研究院 | Cobaltosic oxide micro-nano composite structure array and manufacturing method thereof |
| CN102849785B (en) * | 2012-10-08 | 2014-05-14 | 南京大学 | Preparation method of ZnxCd1-xS ternary composite micrometer hollow sphere |
| CN103074658A (en) * | 2012-12-31 | 2013-05-01 | 苏州汶颢芯片科技有限公司 | Method for electrochemically preparing sea urchin-shaped zinc oxide nanowire array on indium tin oxide (ITO) glass |
| CN105712280A (en) * | 2016-02-03 | 2016-06-29 | 中国科学院合肥物质科学研究院 | Metal oxide hollow sphere array film and preparation method thereof |
| GB201704950D0 (en) * | 2017-03-28 | 2017-05-10 | Univ Manchester | Thin film material transfer method |
| CN108483393A (en) * | 2018-03-12 | 2018-09-04 | 中国科学院合肥物质科学研究院 | Nano-colloid motor and preparation method thereof |
| CN109264664B (en) * | 2018-09-10 | 2020-11-03 | 武汉大学 | Al (aluminum)2O3Preparation method of hollow spherical shell array |
| CN109570490B (en) * | 2018-12-28 | 2021-01-22 | 中国科学院合肥物质科学研究院 | Preparation method of sea urchin-shaped hollow gold nanometer cap with controllable pure surface morphology |
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| CN1730150A (en) * | 2004-08-04 | 2006-02-08 | 中国科学院化学研究所 | A kind of preparation method of the controllable hollow nanometer gold goal based on polymeric vesicle mold |
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| Fengqiang Sun et al..Photochemical Preparation of Two-Dimensional Gold Spherical Pore and Hollow Sphere Arrays on a Solution Surface.《Angew. Chem. Int. Ed.》.2006,第46卷第773-777页. |
| General and Simple Route to Micro/Nanostructured Hollow-Sphere Arrays Based on Electrophoresis of Colloids Induced by Laser Ablation in Liquid;Shikuan Yang et al.;《Langmuir》;20090508;第25卷(第14期);第8287-8291页 * |
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